U.S. patent number 6,045,917 [Application Number 09/114,022] was granted by the patent office on 2000-04-04 for ink jet recording element.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to David E. Decker, Gregory E. Missell.
United States Patent |
6,045,917 |
Missell , et al. |
April 4, 2000 |
Ink jet recording element
Abstract
An ink jet recording element comprising a support having
thereon, in the order recited, a base layer comprising a
hydrophilic material and an ink-receptive top layer comprising a
mordant polymer having the following formula: ##STR1## wherein: A
represents units of an addition polymerizable monomer containing at
least two ethylenically unsaturated groups; B represents units of a
copolymerizable, .alpha.,.beta.-ethylenically unsaturated monomer;
Q is N or P; R.sub.1, R.sub.2 and R.sub.3 each independently
represents a carbocyclic or alkyl group; M.sup.- is an anion; x is
from about 0.25 to about 5 mole percent; y is from about 0 to about
90 mole percent; and z is from about 10 to about 99 mole
percent.
Inventors: |
Missell; Gregory E. (Penfield,
NY), Decker; David E. (Rochester, NY) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
22352933 |
Appl.
No.: |
09/114,022 |
Filed: |
July 10, 1998 |
Current U.S.
Class: |
428/32.29;
428/478.2; 428/478.4; 428/480; 428/500; 428/507; 428/522 |
Current CPC
Class: |
B41M
5/5245 (20130101); Y10T 428/31935 (20150401); Y10T
428/31768 (20150401); Y10T 428/31786 (20150401); Y10T
428/31772 (20150401); Y10T 428/31855 (20150401); Y10T
428/3188 (20150401) |
Current International
Class: |
B41M
5/52 (20060101); B41M 5/50 (20060101); B41M
005/00 () |
Field of
Search: |
;428/411.1,195,478.2,478.4,522,480,500,507 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3958995 |
May 1976 |
Campbell et al. |
5789050 |
August 1998 |
Shaw-Klein et al. |
|
Primary Examiner: Schwartz; Pamela R.
Attorney, Agent or Firm: Cole; Harold E.
Claims
What is claimed is:
1. An ink jet recording element comprising a support having
thereon, in the order recited, a base layer comprising a
hydrophilic material and an ink-receptive top layer comprising a
mordant polymer having the following formula: ##STR6## wherein: A
represents units of an addition polymerizable monomer containing at
least two ethylenically unsaturated groups;
B represents units of a copolymerizable,
.alpha.,.beta.-ethylenically unsaturated monomer;
Q is N or P;
R.sub.1, R.sub.2 and R.sub.3 each independently represents a
carbocyclic or alkyl group;
M.sup.- is an anion;
x is from about 0.25 to about 5 mole percent;
y is from about 0 to about 90 mole percent; and
z is from about 10 to about 99 mole percent.
2. The element of claim 1 wherein A is a repeating unit of an
addition polymerizable monomer containing at least two
ethylenically unsaturated groups having the following structure:
##STR7## wherein n is an integer from 1 to about 10; each R.sub.4
independently represents hydrogen or methyl; and R.sub.5 is a
linking group comprising one or more condensation linkages.
3. The element of claim 1 wherein Q is N, R.sub.1 and R.sub.2 are
each methyl, R.sub.3 is benzyl, A is a unit of a divinylbenzene
monomer, and B is a repeating unit of styrene.
4. The element of claim 1 wherein said mordant polymer is present
at a concentration of about 5% to about 25% by weight of said top
layer.
5. The element of claim 1 wherein said base layer is gelatin,
acetylated gelatin, phthalated gelatin, oxidized gelatin, chitosan,
poly(alkylene oxide), poly(vinyl alcohol), modified poly(vinyl
alcohol), sulfonated polyester, partially hydrolyzed
poly(vinylacetate/vinyl alcohol), poly(acrylic acid),
poly(1-vinylpyrrolidone), poly(sodium styrene sulfonate),
poly(2-acrylamido-2-methane sulfonic acid), or polyacrylamide or
mixtures thereof.
6. The element of claim 1 wherein said base layer comprises
gelatin.
7. The element of claim 1 wherein said base layer has a thickness
of 3 to 20 .mu.m and said top layer has a thickness of 0.1 to 2
.mu.m.
8. The element of claim 1 wherein said base layer, said top layer
or both include matte particles.
9. The element of claim 1 wherein said top layer also contains
methyl cellulose and hydroxyethyl cellulose.
10. The element of claim 9 wherein said hydroxyethyl cellulose is a
cationically modified cellulose ether having the structure:
##STR8## wherein R represents C.sub.n H.sub.2n+1 ;
X represent halide anion; and
y is 1 to about 30.
11. The element of claim 10 wherein y is 1-12 and X is
chloride.
12. The element of claim 10 wherein said cationically modified
cellulose ether is a hydroxyethyl cellulose reacted with
trimethylammonium chloride substituted epoxide or hydroxyethyl
cellulose reacted with a dodecyl dimethylammonium chloride
substituted epoxide.
Description
FIELD OF THE INVENTION
This invention relates to an ink jet recording element.
BACKGROUND OF THE INVENTION
In a typical ink jet recording or printing system, ink droplets are
ejected from a nozzle at high speed towards a recording element or
medium to produce an image on the medium. The ink droplets, or
recording liquid, generally comprise a recording agent, such as a
dye or pigment, and a large amount of solvent. The solvent, or
carrier liquid, typically is made up of water, an organic material
such as a monohydric alcohol, a polyhydric alcohol or mixtures
thereof.
An ink jet recording element typically comprises a support having
on at least one surface thereof an ink-receiving or image-forming
layer, and includes those intended for reflection viewing, which
have an opaque support, and those intended for viewing by
transmitted light, which have a transparent support.
While a wide variety of different types of image-recording elements
for use with ink jet devices have been proposed heretofore, there
are many unsolved problems in the art and many deficiencies in the
known products which have severely limited their commercial
usefulness. The requirements for an image recording medium or
element for ink jet recording are very demanding.
It is well known that in order to achieve and maintain
photographic-quality images on such an image-recording element, an
ink jet recording element must:
Be readily wetted so there is no puddling, i.e., coalescence of
adjacent ink dots, which leads to nonuniform density
Exhibit no image bleeding
Exhibit the ability to absorb high concentrations of ink and dry
quickly to avoid elements blocking together when stacked against
subsequent prints or other surfaces
Provide a high level of gloss and avoid differential gloss
Exhibit no discontinuities or defects due to interactions between
the support and/or layer(s), such as cracking, repellencies, comb
lines and the like
Not allow unabsorbed dyes to aggregate at the free surface causing
dye crystallization, which results in bloom or bronzing effects in
the imaged areas
Have an optimized image fastness to avoid fade from contact with
water or radiation by daylight, tungsten light, or fluorescent
light
It has been observed that in certain ink jet image recording
elements, the imaged or "inked" areas will experience a color or
hue shift when exposed to high humidity and/or slow drying
conditions. This hue shift is also dependent upon the specific ink
sets from different manufacturers. The cause of this hue shift is a
result of the dyes having sufficient moisture in the ink-receiving
layer of the media to allow the dyes to continue to migrate or
spread with time in the ink-receiving layer. An image that is
exposed to high humidity or very slow drying conditions, or covered
after being printed thus slowing drying, will experience a hue or
color shift over time.
DESCRIPTION OF RELATED ART
U.S. Pat. No. 05,789,070, of Shaw-Klein et al., filed Dec. 11, 1996
relates to an ink jet recording element comprising a support coated
with a water-absorbing base coating and an overcoat layer of a
cationically-modified cellulose ether.
While this element provides satisfactory results in most instances,
there is a problem with this element when used at high humidity
and/or slow drying conditions with certain printers and certain
inks. Under such conditions, a hue shift has been observed which is
objectionable.
U.S. Pat. No. 3,958,995 relates to photographic elements containing
cross-linked mordants. However, there is no disclosure in this
patent that these mordants would be useful in an ink jet recording
element.
It is an object of this invention to provide an ink jet recording
element which has less of a color shift when used at high humidity
and/or slow drying conditions.
SUMMARY OF THE INVENTION
This and other objects are provided by the present invention
comprising an ink jet recording element comprising a support having
thereon, in the order recited, a base layer comprising a
hydrophilic material and an ink-receptive top layer comprising a
mordant polymer having the following formula: ##STR2## wherein: A
represents units of an addition polymerizable monomer containing at
least two ethylenically unsaturated groups;
B represents units of a copolymerizable,
.alpha.,.beta.-ethylenically unsaturated monomer;
Q is N or P;
R.sub.1, R.sub.2 and R.sub.3 each independently represents a
carbocyclic or alkyl group;
M.sup.- is an anion;
x is from about 0.25 to about 5 mole percent, preferably 1.0 to 5.0
mole percent;
y is from about 0 to about 90 mole percent, preferably 0 to 45 mole
percent; and
z is from about 10 to about 99 mole percent, preferably 40 to 90
mole percent.
By use of the invention, ink jet recording elements are obtained
which have less of a color shift when used at high humidity and/or
slow drying conditions.
DETAILED DESCRIPTION OF THE INVENTION
The mordant polymer described above may be used in any amount
effective for the intended purpose. In general, good results have
been obtained when the mordant polymer is present in an amount of
about 5% to about 25% by weight of the top layer, preferably about
10%.
The addition of the mordant to the overcoat layer does not degrade
other performance features such as dry time, lightfastness,
coalescence, bleeding, adhesion of the layers, waterfastness, and
gloss when printed with a variety of ink jet inks.
Preferred mordant polymers used in the invention comprise units
having the formula above wherein A is a repeating unit of an
addition polymerizable monomer containing at least two
ethylenically unsaturated groups, such as vinyl groups generally
having the following structure: ##STR3## wherein n is from 1 to
about 10, preferably 2 or 3; each R.sub.4 independently represents
hydrogen or methyl; and R.sub.5 is a linking group comprising one
or more condensation linkages such as amide, sulfonamide, esters
such as sulfonic acid ester, arylene etc., or a condensation
linkage and an organic nucleus such as alkylene, e.g., methylene,
ethylene, trimethylene, arylene, etc.
Suitable monomers from which the repeating units of A are formed
include divinylbenzene, allyl acrylate, allyl methacrylate,
N-allylmethacrylamide, etc.
B in the above formula is a unit of a copolymerizable
.alpha.,.beta.-ethylenically unsaturated monomer (including two,
three or more repeating units), such as ethylene, propylene,
1-butene, isobutene, 2-methylplentene, etc. A preferred class of
ethylenically unsaturated monomers which may be used include the
lower 1-alkenes having from 1 to about 6 carbon atoms; styrene, and
tetramethylbutadiene and methyl methacrylate.
R.sub.1, R.sub.2 and R.sub.3 in the above formula each
independently represents a carbocyclic group such as aryl, aralkyl,
and cycloalkyl such as benzyl, phenyl, p-methyl-benzyl,
cyclopentyl, etc.; or an alkyl group preferably containing from 1
to about 20 carbon atoms such as methyl, ethyl, propyl, isobutyl,
pentyl, hexyl, heptyl, decyl, etc. In a preferred embodiment,
R.sub.1 and R.sub.2 are methyl and R.sub.3 is benzyl.
M.sup.- in the above formula is an anion, i.e., a negative salt
forming an ionic radical or atom such as a halide, e.g., bromide or
chloride, sulfate, alkyl sulfate, alkane or arene sulfonate,
acetate, phosphate, etc.
Further examples of the mordant polymers useful in the invention
and preparation of the above polymers are found in U.S. Pat. No.
3,958,995, the disclosure of which is hereby incorporated by
reference. Specific examples of the major components of such
mordant polymers include the following:
__________________________________________________________________________
##STR4## Mordant A B R.sub.1 R.sub.2 R.sub.3
__________________________________________________________________________
1 C.sub.6 H.sub.4 (CH.dbd.CH.sub.2).sub.2 C.sub.6 H.sub.5 --
CH.sub.3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 CH.dbd.CH.sub.2 2
C.sub.6 H.sub.4 (CH.dbd.CH.sub.2).sub.2 C.sub.6 H.sub.5 -- CH.sub.3
CH.sub.3 CH.sub.3 CH.dbd.CH.sub.2 3 C.sub.6 H.sub.4
(CH.dbd.CH.sub.2).sub.2 C.sub.6 H.sub.5 -- CH.sub.3 CH.sub.3
(CH.sub.3).sub.2 -- CH.dbd.CH.sub.2 CHCH.sub.2 4 C.sub.6 H.sub.4
(CH.dbd.CH.sub.2).sub.2 C.sub.6 H.sub.5 -- (CH.sub.3).sub.2 --
(CH.sub.3).sub.2 -- (CH.sub.3).sub.2 -- CH.dbd.CH.sub.2 CHCH.sub.2
CHCH.sub.2 CHCH.sub.2 OH 5 C.sub.6 H.sub.4 (CH.dbd.CH.sub.2).sub.2
H.sub.2 C.dbd.C(CH.sub.3) CH.sub.3 CH.sub.3 CH.sub.2 C.sub.6
H.sub.5 -- CO.sub.2 --CH.sub.3 OH 6 (H.sub.2 C.dbd.C(CH.sub.3)--
H.sub.2 C.dbd.C(CH.sub.3) CH.sub.3 CH.sub.3 CH.sub.2 C.sub.6
H.sub.5 CO.sub.2 CH.sub.2).sub.2 CO.sub.2 --CH.sub.3
__________________________________________________________________________
Other compatible polymers and/or fillers may be added to the top
coat of the recording element of the invention to enhance
particular performance aspects dependent upon the end use. Polymers
which may be used include nonionic cellulose ethers, anionic
cellulose ethers, polyvinyl alcohol, sulfonated polyesters,
polyvinylpyrrolidone and the like. The top layer generally has a
thickness of about 0.1 to about 2.0 .mu.m.
For example, the top layer of the recording element of the
invention may contain, in addition to the mordant polymer, other
materials such as methyl cellulose, e.g., A4M (Dow Chemical Co.)
and hydroxyethyl cellulose, such as JR400 (hydroxyethyl cellulose
reacted with a trimethyl ammonium chloride substituted epoxide from
Amerchol Corp.) in a weight ratio of 80/20. These materials may be
used in amounts from about 0.75 g/m.sup.2 to about 1.25 g/m.sup.2,
preferably from about 1 g/m.sup.2 to about 1.1 g/m.sup.2.
In a preferred embodiment of the invention, the hydroxyethyl
cellulose employed is a cationically-modified cellulose ether as
described in U.S. Pat. No. 5,789,070, of Shaw-Klein et al., filed
Dec. 11, 1996, having the structure: ##STR5## wherein R represents
C.sub.n H.sub.2n+1 ;
X represent halide anion; and
y is 1 to about 30.
The top layer may contain about 5 to about 75 weight percent of the
cationically-modified cellulose ether described above. Useful
cationically-modified cellulose ether polymers include Celquat.RTM.
SC240C (hydroxyethyl cellulose reacted with trimethylammonium
chloride substituted epoxide from National Starch and Chemical Co.)
and Quatrisoft.RTM. LM-200 (hydroxyethyl cellulose reacted with a
dodecyl dimethylammonium chloride substituted epoxide from Amerchol
Corp.).
The base layer is primarily intended to act as a sponge layer for
the absorption of ink solvent. As such, it is primarily composed of
hydrophilic or porous materials. Generally, the base layer has a
thickness of about 3 to about 20 .mu.m, and is present in an amount
from about 5 g/m.sup.2 to about 7 g/m.sup.2, preferably from about
5.3 g/m.sup.2 to about 5.5 g/m.sup.2. Suitable hydrophilic
materials include gelatin, acetylated gelatin, phthalated gelatin,
oxidized gelatin, chitosan, poly(alkylene oxide), poly(vinyl
alcohol), modified poly(vinyl alcohol), sulfonated polyester,
partially hydrolyzed poly(vinylacetate/ vinyl alcohol),
poly(acrylic acid), poly(1-vinylpyrrolidone), poly(sodium styrene
sulfonate), poly(2-acrylamido-2-methane sulfonic acid), or
polyacrylamide or mixtures thereof. Copolymers of these polymers
with hydrophobic monomers may also be used.
The pH of the base layer may be adjusted to optimize swelling
(water capacity), to enhance gloss or to minimize dye migration.
For example, the pH of the layer may be reduced to 3.5 to improve
swelling capacity, thereby reducing ink drying times, and to impart
waterfastness. In another embodiment, the pH of the image recording
layer may be raised to 8.5 in order to enhance gloss and reduce
bronzing due to surface dye crystallization.
In a preferred embodiment of the invention, the base layer is
50%-100% photographic-grade gelatin, modified so that the pH is far
from the isoelectric point of the gelatin, so that water uptake may
be maximized. The remainder of the layer may consist of a polymer
or inorganic material compatible with the gelatin which does not
adversely impact functional properties.
If desired, the base layer of the recording element of the
invention may be made porous by the addition of ceramic or hard
polymeric particulates, by foaming or blowing during coating, or by
inducing phase separation in the layer through introduction of a
nonsolvent. In addition, rigidity may be imparted to the base layer
through incorporation of a second phase such as polyesters,
poly(methacrylates), polyvinyl benzene- containing copolymers and
the like.
In the present invention, the recording element can be opaque,
translucent, or transparent. Thus, the supports utilized in the
recording element of the present invention are not particularly
limited and various supports may be employed. Accordingly, plain
papers, resin-coated papers, various plastics including a
polyester-type resin such as poly(ethylene terephthalate),
poly(ethylene naphthalate) and polyester diacetate, a
polycarbonate-type resin, a fluorine-type resin such as
polytetrafluoroethylene, metal foil, various glass materials, and
the like can be employed as supports. When the supports of the
present invention are transparent, a transparent recording element
can be obtained and used as a transparency in an overhead
projector. The thickness of the support employed in the invention
can be from about 12 to about 500 .mu.m, preferably from about 75
to about 300 .mu.m.
If desired, in order to improve the adhesion of the base layer to
the support, the surface of the support may be
corona-discharge-treated prior to applying the base layer or
solvent-absorbing layer to the support. Alternatively, an
under-coating, such as a layer formed from a halogenated phenol or
a partially hydrolyzed vinyl chloride-vinyl acetate copolymer can
be applied to the surface of the support.
Since the image recording element may come in contact with other
image recording articles or the drive or transport mechanisms of
image recording devices, additives such as surfactants, lubricants,
matte particles and the like may be added to the element to the
extent that they do not degrade the properties of interest.
The layers described above, including the base layer and the top
layer, may be coated by conventional coating means onto a support
material commonly used in this art. Coating methods may include,
but are not limited to, wound wire rod coating, slot coating, slide
hopper coating, gravure, curtain coating and the like. Some of
these methods allow for simultaneous coatings of both layers, which
is preferred from a manufacturing economic perspective.
Ink jet inks used to image the recording elements of the present
invention are well-known in the art. The ink compositions used in
ink jet printing typically are liquid compositions comprising a
solvent or carrier liquid, dyes or pigments, humectants, organic
solvents, detergents, thickeners, preservatives, and the like. The
solvent or carrier liquid can be solely water or can be water mixed
with other water-miscible solvents such as polyhydric alcohols.
Inks in which organic materials such as polyhydric alcohols are the
predominant carrier or solvent liquid may also be used.
Particularly useful are mixed solvents of water and polyhydric
alcohols. The dyes used in such compositions are typically
water-soluble direct or acid type dyes. Such liquid compositions
have been described extensively in the prior art including, for
example, U.S. Pat. Nos. 4,381,946; 4,239,543 and 4,781,758, the
disclosures of which are hereby incorporated by reference.
Although the recording elements disclosed herein have been referred
to primarily as being useful for ink jet printers, they also can be
used as recording media for pen plotter assemblies. Pen plotters
operate by writing directly on the surface of a recording medium
using a pen consisting of a bundle of capillary tubes in contact
with an ink reservoir .
The following example further illustrates the invention.
EXAMPLE
Element 1--Control
This recording element was prepared by slot coating. The base layer
was coated from a 10% solids aqueous formulation directly on corona
discharge-treated, photographic grade, polyethylene-coated paper
and dried thoroughly at 100.degree. C. The final dry coverage of
the base layer was 5.4 g/m.sup.2. The image recording layer (top
layer) was coated directly over the base layer in a second pass
from coating formulations ranging from 1 to 2% solids. The latter
layer was dried under identical conditions to the base layer. The
dry coverage of the image receiving layer (top layer) was 1.1
g/m.sup.2.
The base layer of the element was a mixture of 60% by weight
lime-process ossein photographic grade gelatin, 30%
polyvinylpyrrolidone (PVP K-90, ISP) and 10% by weight of mordant
C-2 (see below). The pH of the coating formulation was adjusted to
3.5 by direct addition of hydrochloric acid (36-38%, J T
Baker).
The top layer of the element was a 20/80% mixture of methyl
cellulose (A4M) (Dow Chemical Co.) and hydroxyethyl cellulose
(Quatrisoft.RTM. LM200, Amerchol Corp.).
The following closely-related comparison mordants were used in the
comparison elements to illustrate that not all mordants are
useful:
C-1: poly(N,N-dimethylcyclohexyl vinylbenzyl) ammonium chloride
C-2: poly(N-vinyl benzyl-N,N,N-trimethyl ammonium
chloride-co-ethyleneglycol dimethacrylate)
Element 2--Comparison
This element is the same as Control Element 1 except that
comparison mordant C-1 was added to the top coat layer at 10% by
weight and coated over the base as described above. The surfactants
Olin 10 G (Dixie Chemicals Corp.) and FS-300 (Zonyl.RTM., DuPont
Corp.) were added to help coatability.
Element 3--Comparison
This element is the same as Element 2 except that comparison
mordant C-2 was used.
Element 4--Invention
This element is the same as Element 1 except that mordant 1 was
used.
Each element was then imaged on an Epson 600 Ink Jet Printer at
300.times.600 dpi with Standard Epson 600 Inks, cyan, magenta and
yellow (U.S. Pat. Nos. 5,158,377; 5,221,148 and 5,421,658) and a
Lexmark 7000 Ink Jet Printer at 300.times.600 dpi with Lexmark
Photo Inks, cyan, magenta and yellow (U.S. Pat. Nos. 5,364,461;
5,254,160 and 5,497,178). One print was dried at 21.degree. C. and
50% RH for 24 hours, and another print was dried at 26.degree. C.
and 80% RH for 24 hours.
To measure the hue shift, the color space system, measuring the
axis of L*, a*, b* was used. The a* and b* values, which measure
the hue shift, where a* goes from -a, being green, to +a being red;
and -b, being blue, to +b being yellow, were measured at both
drying conditions. The delta of the two drying conditions was then
calculated to show the shift along the "a" and "b" axis. The + or -
sign of the delta indicates the color of the shift on each axis and
the absolute value indicates the magnitude of the shift. The
smaller the delta, the less of a hue shift. The results are shown
in the following Tables:
TABLE 1 ______________________________________ Lexmark 7000 Printer
Drying @ 21.degree. C., Drying @ 26.degree. C., Element 50% RH 80%
RH (Mordant) a* b* a* b* Delta a* Delta b*
______________________________________ 1 (None) -8.1 2.3 -12.3 19.0
-4.2 16.7 2 (C-1) -9.8 4.1 -11.8 15.7 -2 11.6 3 (C-2) 8.3 8.9 10.4
11.6 -2.1 2.7 4 (1) -9.3 -0.6 -10.2 1.0 -0.9 1.6
______________________________________
TABLE 2 ______________________________________ Epson 600 Printer
Drying @ 21.degree. C., Drying @ 26.degree. C., Element 50% RH 80%
RH (Mordant) a* b* a* b* Delta a* Delta b*
______________________________________ 1 (None) -9.4 2.7 -16 21.5
-6.6 18.8 2 (C-1) -10.3 -7.2 -12.7 -4.5 -2.4 2.7 3 (C-2) -10 1.3
-12 3.7 -2 2.4 4 (1) -8.9 -8.2 -9.1 -7.1 -0.2 1.1
______________________________________
The above results show that use of the mordant of the invention had
a much smaller hue shift (Delta a* and Delta b*) than the control
element with no mordant and the comparison elements with the
comparison mordants.
This invention has been described with particular reference to
preferred embodiments thereof but it will be understood that
modifications can be made within the spirit and scope of the
invention.
* * * * *